CN114824199A - Silicon carbide-silicon-graphite composite material and preparation method and application thereof - Google Patents
Silicon carbide-silicon-graphite composite material and preparation method and application thereof Download PDFInfo
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- 239000010703 silicon Substances 0.000 title claims abstract description 115
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910003474 graphite-silicon composite material Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
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- 239000010439 graphite Substances 0.000 claims abstract description 73
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 42
- 239000002131 composite material Substances 0.000 claims abstract description 41
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 35
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- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 30
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- 239000000463 material Substances 0.000 claims abstract description 10
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- 238000000034 method Methods 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
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- 239000010410 layer Substances 0.000 claims description 13
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
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- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000011868 silicon-carbon composite negative electrode material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- OOCUOKHIVGWCTJ-UHFFFAOYSA-N chloromethyl(trimethyl)silane Chemical compound C[Si](C)(C)CCl OOCUOKHIVGWCTJ-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
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- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The invention discloses a silicon carbide-silicon-graphite composite material and a preparation method and application thereof. The silicon carbide-silicon-graphite composite material takes graphite particles as a base material, and the nano silicon and the silicon carbide coating layer are generated in situ on the surface of the graphite particle by a CVD method, so that the nano silicon is uniformly dispersed and has high bonding strength with graphite, the stability and the electrochemical activity of the composite material are greatly improved, the silicon carbide is adopted as the coating layer, the coating thickness can be improved compared with an amorphous carbon coating layer, the silicon carbide coating with a crystal structure is firmer, and the stability of the composite material is greatly improved.
Description
Technical Field
The invention relates to a silicon-carbon composite material, in particular to a silicon carbide-silicon-graphite composite material, a method for preparing the silicon carbide-silicon-graphite composite material by vapor deposition, and application of the silicon carbide-silicon-graphite composite material in a lithium ion battery cathode material, belonging to the technical field of preparation of the lithium ion battery cathode material.
Background
The lithium ion battery has higher capacity and good stability, has extremely important function in the fields of portable electronic devices and electric automobiles, and along with the progress and development of the industry, the social demand for novel power sources is increased greatly, and among a plurality of lithium ion battery cathode materials, the lithium ion battery cathode material is compared with the traditional graphite cathode material (372 mAhg. about. -1 ) The silicon material has extremely high theoretical capacity (-4200 mAhg) -1 ) And a lower potential for lithium: (<0.5V vs Li/Li + ) Therefore, the silicon material has excellent development prospect in the field of lithium batteries. However, the silicon-based negative electrode material has a serious problem of volume expansion in the process of lithium intercalation and deintercalation, which results in a great reduction in the capacity of the negative electrode, so that the silicon material has a short cycle life as the negative electrode material, and the silicon material has a low conductivity as a semiconductor, which are not favorable for the use of the silicon material in a lithium ion battery.
In order to solve the problem of the silicon material in the lithium ion battery, the silicon material is subjected to nanocrystallization to prepare a plurality of silicon with nano-structure forms, such as nano-particles, nano-wires and nano-tubes, so that the problem can be solved, and the material failure caused by expansion of the silicon material in the charging and discharging processes can be reduced. For the practical application of nano-silicon, compounding silicon material with graphite into carbon-silicon composite material has been emphasized as a reasonable strategy, rather than using silicon-based material to achieve high energy density. The silicon material with a nano-sized structure can be prepared on the surface of graphite by using a CVD method, and the nano-silicon material prepared by using the CVD method can be used for controlling the growth size and the appearance of the silicon material and the content of the silicon material in a negative electrode material, so that the method is an excellent method for preparing the nano-silicon material. However, these silicon-graphite composites have limited specific capacities and limited silicon content. Otherwise, excessive deposition of Si results in thickening of the Si nanolayer on the graphite, leading to accelerated degradation of cycle performance and a reduction in the advantages of nanocrystallization. Meanwhile, the silicon material is coated, so that the influence caused by the expansion of the silicon material can be reduced, and the specific surface area of graphite can be effectively reduced, thereby reducing the lithium ion loss of the silicon-carbon composite negative electrode material in the first cycle process.
Most of the existing CVD preparation silicon-carbon composite materials usually need a plurality of working procedures, a plurality of heating processes and cooling processes are needed, a silicon source and a carbon source are changed to carry out a plurality of depositions to obtain a final product, the preparation process of the materials is often too complicated, the CVD preparation silicon-carbon composite materials are not beneficial to wider application of the CVD preparation silicon-carbon composite materials, and the development of the CVD preparation silicon-carbon composite materials with simpler steps has great significance for the application of the silicon-based materials in lithium ion batteries.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a silicon carbide-silicon-graphite composite material, the composite material takes graphite as a base material, nano silicon and a silicon carbide coating layer are generated in situ on the surface of the graphite by a CVD method, the nano silicon is uniformly dispersed, the bonding strength with the graphite is high, and the stability and the electrochemical activity of the composite material are greatly improved.
The second purpose of the invention is to provide a preparation method of the silicon carbide-silicon-graphite composite material, which can be completed by only one CVD process in the process of depositing the nano-silicon and the silicon carbide coating layer, simplifies the process, overcomes the defect that multiple vapor deposition steps are often needed to complete the deposition of different components in the process of preparing the silicon carbon composite material by CVD in the prior art, and the complicated deposition process limits the wide application of the coated carbon silicon composite material.
The third purpose of the invention is to provide an application of the silicon carbide-silicon-graphite composite material, and the silicon carbide-silicon-graphite composite material is used as a lithium ion negative electrode material, so that a lithium ion battery with high lithium storage capacity and good cycle stability can be obtained.
In order to achieve the technical purpose, the invention aims to provide a preparation method of a silicon carbide-silicon-graphite composite material, which comprises the steps of sequentially generating a nano silicon layer and a silicon carbide layer on the surface of graphite particles or a composite of the graphite particles and a metal catalyst through chemical vapor deposition, and then volatilizing at high temperature or removing the metal catalyst through acid washing to obtain the silicon carbide-silicon-graphite composite material.
According to the technical scheme, a metal catalyst is compounded with graphite particles, a silicon nano material (silicon nano particles or silicon nano fibers and the like) is generated in situ on the surface of the graphite by a vapor deposition method under the catalytic action of the metal catalyst, or a silicon nano film is directly deposited on the surface of the graphite particles without adding the catalyst, a silicon carbide coating layer is deposited, two kinds of deposits can be completed by one-time CVD deposition process, and the metal catalyst is removed by high-temperature volatilization to obtain the pure silicon carbide-silicon-graphite composite material. In the prior art, in the process of preparing the silicon-carbon composite material with the coating structure by a vapor deposition method, multiple vapor deposition steps are often needed to complete the deposition process of different materials, and the complex deposition process limits the production process of the coating type carbon-silicon composite material. The carbon-silicon composite material designed in the technical scheme of the invention takes graphite particles as a carrier, nano-silicon as an active substance and silicon carbide as a coating layer, and the generation process of the nano-silicon and the silicon carbide can be completed in the same CVD deposition system by simply adjusting the silicon-carbon atom ratio, the deposition temperature and the like, so that the preparation process of the coating type silicon-carbon composite material is simplified.
As a preferable mode, the graphite particles and metal-based catalyst composite is obtained by wet mixing a metal-based catalyst and graphite particles. In general, the metal-based catalyst and the graphite particles may be mixed by a dry mixing method or a wet mixing method. The dry mixing is to directly mechanically mix the graphite particles and the metal catalyst, such as grinding, ball milling and the like. The wet mixing is mainly to dissolve the metal catalyst in the solvent, mix with the graphite particles in the condensation process, and dry. Preferably, the wet mixing is performed, and the metal catalyst can be uniformly supported on the surface of the graphite particles.
In a preferred embodiment, the metal-based catalyst is a metal compound containing at least one of iron, nickel, copper, and cobalt. The metal catalyst is soluble salt of iron, nickel, copper, cobalt, etc., such as ferric chloride, nickel nitrate, copper sulfate, cobalt chloride, etc.
As a preferred aspect, the graphite particles are artificial graphite and/or natural graphite. Such as spherical graphite, flake graphite, expanded graphite, etc.
In a preferred embodiment, the mass of the metal catalyst is 1 to 10% of the total mass of the graphite particles and the metal catalyst composite, and if the content of the metal catalyst is less than 1%, the amount of the active material deposited in situ on the surface of the graphite particles is reduced, and the electrode capacity of the graphite is reduced by the excessive metal catalyst. More preferably, the mass of the metal catalyst is 2% to 6% of the total mass of the graphite particles and the metal catalyst composite.
As a preferable scheme, the chemical vapor deposition conditions for generating the nano silicon are as follows: one or more of silane, methylsilane, chlorosilane and chloromethylsilane are used as silicon sources, the atmosphere is hydrogen atmosphere, the temperature is 500-1100 ℃, and the time is 1-3 hours; the nano silicon is silicon nano particles, silicon nano films or silicon nano fibers. The shape of the generated nano silicon is related to the selected silicon source raw materials, deposition temperature, deposition time and other conditions, for example, under the same deposition conditions, the higher the silicon-hydrogen ratio, the more the silicon-hydrogen ratio tends to generate silicon nanofibers, for example, when the ratio of silicon atoms to hydrogen atoms in the vapor deposition process is 1:2, silicon nanoparticles are mainly generated, and when the ratio of silicon atoms to hydrogen atoms is 2:1, silicon nanofibers are mainly generated. The silicon source is mainly gaseous silicon-containing small molecular compound, specifically silane such as monosilane, disilane, etc., chlorosilane such as monochlorosilane, chloromethylsilane such as (chloromethyl) trimethylsilane
As a preferable scheme, the chemical vapor deposition conditions for generating the silicon carbide layer are as follows: silane is used as a silicon source, at least one of methane, ethane, propane, isopropane, butane, isobutane, ethylene, propylene, acetylene and methane is used as a carbon source, or at least one of methylsilane, chlorosilane and chloromethylsilane is used as the silicon source and the carbon source at the same time, the atmosphere is an inert atmosphere, the molar ratio of the silicon source to the carbon source is measured according to the molar ratio of silicon atoms to carbon atoms of not less than 1:2, the temperature is 600-1500 ℃, and the time is 0.5-3 hours. The vapor deposition pressure may be negative, positive or normal. Generally, the silicon-carbon composite material adopts a carbon coating layer, but an amorphous carbon layer which does not form a stable carbon crystal structure is deposited by CVD, so that a thicker carbon coating layer is difficult to form on the surface of a microparticle, and the thickness of the carbon coating layer is often less than 100 nm; the silicon carbide coating can form a stable crystal structure during deposition, and a silicon carbide coating layer formed by aggregation of a tiny silicon carbide crystal particle is formed (as shown in the description of fig. 2d), so that the silicon carbide can have a higher thickness, and the thickness is more than 200 nm. An inert atmosphere such as argon.
As a preferable embodiment, the conditions of the high-temperature volatilization demetallization catalyst are as follows: the temperature is 1500-2500 ℃, and the time is 0.5-2 hours. The high-efficiency volatilization and removal of the metal catalyst can be realized under the optimized conditions.
As a preferred embodiment, the conditions for removing the metal-based catalyst by acid washing are as follows: washing with 0.1-2 mol/L dilute hydrochloric acid or dilute sulfuric acid.
Preferably, the thickness of the single layer of the silicon carbide layer is 0.1-1.0 μm.
The invention also provides a silicon carbide-silicon-graphite composite material which is prepared by the preparation method.
The silicon carbide-silicon-graphite composite material takes the graphite particles as a base material, and the nano silicon and the silicon carbide coating layer are generated in situ on the surfaces of the graphite particles by a CVD method, the nano silicon is uniformly dispersed on the surfaces of the graphite particles, the bonding strength between the nano silicon and the graphite particles is high, the stability and the electrochemical activity of the composite material are greatly improved, and the silicon carbide is taken as the coating layer, so that the silicon carbide-silicon-graphite composite material has higher coating thickness which can reach 100-200 nm and even more than 200nm compared with a common amorphous carbon coating layer, and the SiC coating layer with a crystal structure is firmer, and the stability of the composite material is greatly improved.
The invention also provides an application of the silicon carbide-silicon-graphite composite material as a negative electrode material of a lithium ion battery.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. according to the technical scheme, the nano silicon and the graphite particles in the silicon carbide-silicon-graphite composite material are compounded in situ by a chemical vapor deposition method, the nano silicon is uniformly dispersed and has high bonding strength with the graphite particles, the stability and the electrochemical activity of the composite material are greatly improved, the silicon carbide layer generated in situ is used as a coating layer, the silicon carbide layer is used as the coating layer, and compared with a common amorphous carbon coating layer, the silicon carbide-silicon-graphite composite material has higher coating thickness which can reach 100-200 nm, the SiC coating layer with a crystal structure is firmer, the silicon carbide layer can effectively relieve the volume effect brought by the silicon in a circulation process, the stability of the composite material is greatly improved, and the performance and the service life of a battery are improved.
2. In the preparation process of the silicon carbide-silicon-graphite composite material, the active substance nano silicon and the silicon carbide coating layer can be generated in the one-time CVD deposition process, so that the heat loss in the production process is reduced, and the preparation flow of the coated silicon-carbon composite material is simplified.
3. The preparation method of the silicon carbide-silicon-graphite composite material provided by the technical scheme of the invention is simple in process, low in cost and easy for industrial production.
4. The silicon carbide-silicon-graphite composite material is prepared by a chemical vapor deposition method, has the characteristics of controllable silicon size, shape and loading capacity and controllable silicon carbide coating thickness, and can be used for preparing silicon-carbon composite cathode materials with different performance requirements according to design requirements.
Drawings
FIG. 1 is an XRD pattern of pure graphite G, silicon-graphite composite Si/G, silicon carbide-graphite composite SiC @ G, silicon carbide-silicon-graphite composite SiC @ Si/G (example 1).
FIG. 2 is a scanning electron micrograph; wherein, a is pure graphite G, b which is silicon carbide-graphite composite SiC @ G, c which is silicon-graphite composite Si/G, d which is silicon carbide-silicon-graphite composite SiC @ Si/G.
FIG. 3 shows the cycle curves of lithium ion batteries of pure graphite G, silicon-graphite composite material Si/G, silicon carbide-graphite composite material SiC @ G and silicon carbide-silicon-graphite composite material SiC @ Si/G, in which CR2032 half-cell test is adopted, and lithium metal is a counter electrode.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
1. Weighing 50g of graphite powder and 2g of ferric chloride, mixing in an aqueous solution, drying for 12 hours at 80 ℃ in a forced air drying oven, grinding, and sieving by a 200-mesh sieve. And (3) placing the sample in a chemical vapor deposition furnace, taking trichloromethylsilane as a silicon source, setting the deposition atmosphere as a hydrogen atmosphere, and depositing for 1h at the temperature of 800 ℃ under normal pressure to obtain the silicon nanofiber-graphite composite material.
2. And (3) in the same vapor deposition furnace, raising the temperature to 900 ℃, taking trichloromethylsilane as a silicon source and a carbon source, taking argon as a carrier gas, setting the deposition atmosphere as an argon atmosphere, depositing for 0.5h, then placing in a high-temperature furnace for heat treatment at 1500 ℃ for 0.5h, removing trace elements to prepare the silicon carbide-silicon nanofiber-graphite composite material, grinding the deposited sample, washing with deionized water for three times, carrying out suction filtration and drying, and preparing to obtain the silicon carbide-silicon nanofiber-graphite composite material (d).
The XRD pattern of the prepared silicon carbide-silicon-graphite composite material is shown in figure 1, and compared with the diffraction peak of a graphite substrate, the silicon carbide-silicon-graphite composite material has obviously more characteristic peaks of silicon and silicon carbide, which indicates the success of silicon deposition and the successful coating of the silicon carbide.
The scanning electron microscope image of the prepared silicon carbide-silicon-graphite composite material is shown in fig. 2, wherein a in fig. 2 is the electron microscope image of a single graphite particle, c in fig. 2 is a sample obtained by silicon fiber deposition, silicon fibers are densely and alternately distributed on the graphite surface, b in fig. 2 is the sample morphology after silicon carbide coating, and d in fig. 2 is the sample morphology of the silicon carbide-silicon-graphite composite material after silicon deposition and silicon carbide deposition.
The composite negative electrode material, the conductive carbon black and the adhesive PVDF are mixed according to the proportion of 7: 1:2, preparing a negative electrode material, taking lithium metal as a counter electrode, adopting a Celgard2400 polypropylene porous diaphragm, adopting an electrolyte solution of LiPF6 solution of 1mol/L, and preparing a CR2032 half-cell test by using an organic solvent which is a mixture with the volume ratio of EC to DMC of 1 to 1, wherein the test current density is 100 mA/g.
The cycle performance curve of the silicon carbide-silicon-graphite composite material is shown in fig. 3, the reversible specific capacity of the graphite G after 100 cycles of circulation is 330mAh/G, the reversible specific capacity of the silicon carbide-silicon-graphite composite material after 100 cycles of circulation is 490mAh/G, and the capacity is hardly changed any more, because the growth of the silicon nanofibers improves the lithium storage capacity of the material, and the coating of the silicon carbide layer improves the cycle stability of the composite material.
Comparative example 1
1. Weighing 50g of graphite powder and 2g of ferric chloride, mixing in an aqueous solution, drying for 12h at 80 ℃ in a forced air drying oven, grinding, and sieving by a 200-mesh sieve. And (3) placing the sample in a chemical vapor deposition furnace, taking trichloromethylsilane as a silicon source, setting the deposition atmosphere as a hydrogen atmosphere, and depositing for 1h at the temperature of 800 ℃ under normal pressure to obtain the silicon nanofiber-graphite composite material.
2. And (3) placing the silicon carbide-free sample in a high-temperature furnace for heat treatment at 1500 ℃ for 0.5h, removing trace elements to prepare the silicon carbide-free carbon-silicon composite material, grinding the deposit sample, washing with deionized water for three times, performing suction filtration, and drying to prepare the silicon nanofiber-graphite composite material (c).
The prepared silicon-carbon composite negative electrode material is assembled into a lithium battery according to the embodiment 1, the specific capacity of the lithium battery is only 327mAh/G after 100 cycles, and as shown in a Si/G curve of fig. 3, compared with the capacity of a carbon-silicon composite material coated by silicon carbide, the capacity of the lithium battery is greatly reduced after multiple cycles, because the silicon material is subjected to violent volume expansion and pulverization under the condition that no silicon carbide layer exists, so that the failure is caused, and the integral capacity of the composite material is reduced.
Comparative example 2
1. Weighing 50g of graphite powder and 2g of ferric chloride, mixing in an aqueous solution, drying for 12h at 80 ℃ in a forced air drying oven, grinding, and sieving by a 200-mesh sieve. And (2) placing the sample in a chemical vapor deposition furnace, setting the temperature to be 900 ℃, taking trichloromethylsilane as a silicon source and a carbon source, taking argon as a carrier gas, setting the deposition atmosphere to be an argon atmosphere, depositing for 0.5h, then placing in a high-temperature furnace for heat treatment at 1500 ℃ for 0.5h, removing trace elements to prepare the silicon carbide-silicon nanofiber-graphite composite material, grinding the deposited sample, washing with deionized water for three times, carrying out suction filtration and drying, and preparing to obtain the silicon carbide-graphite composite material (b).
The prepared silicon carbide-graphite composite negative electrode material is assembled into a lithium battery according to example 1, the capacity of the lithium battery in the first cycle is 343mAh/G, and the capacity of the lithium battery after one hundred cycles is 330mAh/G, as shown in a SiC @ G curve of FIG. 3. Compared with the graphite substrate, the capacity is not obviously changed, which shows that the SiC coating layer does not influence the original capacity.
Example 2
1. Weighing 50g of graphite powder and 2g of nickel nitrate, mixing in an aqueous solution, drying in a forced air drying oven at 80 ℃ for 12h, grinding, and sieving by a 200-mesh sieve. And (3) placing the sample in a chemical vapor deposition furnace, taking silane as a silicon source, setting the deposition atmosphere as a hydrogen atmosphere, and depositing at 600 ℃ for 0.5h under the pressure of-0.1 MPa to obtain the silicon nanoparticle-graphite composite material.
2. Controlling the temperature of a chemical vapor deposition furnace to be 600 ℃, adding acetylene as a carbon source, taking silane as a silicon source, adjusting the ratio of carbon atoms to silicon atoms to be 2:1, taking argon as a carrier gas, setting the deposition atmosphere to be argon atmosphere, depositing for 1h, grinding a deposition sample, washing with deionized water for three times, performing suction filtration and drying, and preparing the silicon carbide-silicon nanoparticle-natural graphite composite material.
3. And then placing the sample in a high-temperature furnace for heat treatment at 1500 ℃ for 0.5h, cooling the sample to room temperature, grinding, washing with deionized water for three times, carrying out suction filtration and drying, and removing trace elements to obtain the silicon carbide-silicon nanoparticle-natural graphite composite material.
The prepared silicon carbide-silicon-natural graphite silicon-carbon composite negative electrode material is assembled into a lithium battery according to the embodiment 1, the first discharge specific capacity is 980mAh/g, and the specific capacity of 560mAh/g is still obtained after 50 cycles.
Example 3
1. 50g of graphite powder is weighed, ground and sieved by a 200-mesh sieve. And (3) placing the sample in a chemical vapor deposition furnace, taking silane as a silicon source, setting the deposition atmosphere as a hydrogen atmosphere, and depositing at 600 ℃ under normal pressure for 0.5h under the pressure of-0.1 MPa to obtain the silicon nano-film-graphite composite material.
2. Controlling the temperature of a chemical vapor deposition furnace to be 600 ℃, adding propylene as a carbon source, using silane as a silicon source, controlling the deposition atmosphere to be argon atmosphere, adjusting the ratio of carbon atoms to silicon atoms to be 2:1, depositing for 0.5h, grinding a deposition sample, washing with deionized water for three times, performing suction filtration and drying, and preparing the silicon carbide-silicon nano film-graphite composite material.
3. The prepared silicon carbide-silicon nano film-graphite composite negative electrode material is assembled into a lithium battery according to the embodiment 1, the first discharge specific capacity is 760mAh/g, and the capacity is 460mAh/g after 50 cycles of circulation.
Example 4
1. Weighing 50g of graphite powder and 2g of nickel nitrate, mixing in an aqueous solution, drying in a forced air drying oven at 80 ℃ for 12h, grinding, and sieving by a 200-mesh sieve. And (3) placing the sample in a chemical vapor deposition furnace, and depositing for 0.5h at 700 ℃ by taking silane as a silicon source to obtain the silicon nanofiber-graphite composite material.
2. Controlling the temperature of a chemical vapor deposition furnace to be 800 ℃, taking dichlorodimethylsilane as a carbon source and a silicon source, setting the atmosphere to be argon atmosphere, depositing for 0.5h, grinding a deposition sample, washing with deionized water for three times, performing suction filtration and drying to prepare the silicon carbide-silicon nanofiber-graphite composite material.
3. And then removing the catalyst from the sample by using 0.5mol/L dilute hydrochloric acid solution, washing the sample with deionized water for three times, performing suction filtration and drying, and removing trace elements to prepare the silicon carbide-silicon nanofiber-natural graphite composite material.
The prepared silicon carbide-silicon nanofiber-graphite composite negative electrode material is assembled into a lithium battery according to example 1, the first discharge specific capacity is 856mAh/g, and the capacity is 558mAh/g after 50 cycles.
Claims (10)
1. A preparation method of a silicon carbide-silicon-graphite composite material is characterized by comprising the following steps: sequentially generating nano silicon and a silicon carbide layer on the surfaces of the graphite particles or the graphite particles and the metal catalyst compound through chemical vapor deposition, and then volatilizing at high temperature or removing the metal catalyst through acid washing to obtain the catalyst.
2. The method of preparing a silicon carbide-silicon-graphite composite material according to claim 1, wherein: the graphite particle and metal catalyst composite is obtained by mixing a metal catalyst and graphite particles by a wet method.
3. The method for preparing a silicon carbide-silicon-graphite composite material according to claim 1 or 2, wherein:
the metal catalyst is a metal compound containing at least one of iron, nickel, copper and cobalt;
the graphite particles are artificial graphite and/or natural graphite.
4. The method of preparing a silicon carbide-silicon-graphite composite material according to claim 1, wherein: the mass of the metal catalyst accounts for 1-10% of the total mass of the graphite particles and the metal catalyst compound.
5. The method of preparing a silicon carbide-silicon-graphite composite material according to claim 1, wherein: the chemical vapor deposition conditions for generating the nano silicon are as follows: one or more of silane, methylsilane, chlorosilane and chloromethylsilane are used as silicon sources, hydrogen is used as atmosphere, the temperature is 500-1100 ℃, and the time is 1-3 hours; the nano silicon is silicon nano particles, silicon nano films or silicon nano fibers.
6. The method of preparing a silicon carbide-silicon-graphite composite material according to claim 1, wherein: the chemical vapor deposition conditions for generating the silicon carbide layer are as follows: silane is used as a silicon source, at least one of methane, ethane, propane, isopropane, butane, isobutane, ethylene, propylene, acetylene and methane is used as a carbon source, or at least one of methylsilane, chlorosilane and chloromethylsilane is used as the silicon source and the carbon source at the same time, the atmosphere is an inert atmosphere, the molar ratio of the silicon source to the carbon source is measured according to the molar ratio of silicon atoms to carbon atoms of not less than 1:2, the temperature is 600-1500 ℃, and the time is 0.5-3 hours.
7. The method of preparing a silicon carbide-silicon-graphite composite material according to claim 1, wherein: the conditions for volatilizing and removing the metal catalyst at high temperature are as follows: the temperature is 1500-2500 ℃, and the time is 0.5-2 hours.
8. The method of preparing a silicon carbide-silicon-graphite composite material according to claim 1, wherein: the thickness of the single layer of the silicon carbide layer is 0.1-1.0 mu m.
9. A silicon carbide-silicon-graphite composite material characterized by: the preparation method of any one of claims 1 to 8.
10. Use of a silicon carbide-silicon-graphite composite material according to claim 9, wherein: the material is applied as a negative electrode material of a lithium ion battery.
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